JP4704038B2 - Sterilization mixture - Google Patents

Description

The present invention
A) Phenylhydrazide I selected from compounds Ia and Ib:

When,
B) Formula II:

And a sterilizing mixture comprising a synergistically effective amount.

  The invention further relates to a method for controlling harmful bacteria using a mixture of compounds I and II, to the use of compounds I and II to produce such a mixture and to compositions comprising them.

The compounds of formula I, their preparation and their action against harmful fungi are known from the literature:

  The compound of formula II (generic name: dithianone) and its preparation are described in GB-A857383.

  However, the bactericidal activity of the known compounds, particularly the durability of phenylhydrazine I, was unsatisfactory.

  The object of the present invention is therefore to overcome the disadvantages mentioned above and to provide improved activity (especially persistence) against harmful bacteria in combination with reducing the total amount of active compound applied (synergistic mixture). It is to provide a sterilization mixture having.

  We have found that this object is achieved by a mixture as defined above. Furthermore, the inventors have noted that applying compounds I and II simultaneously, i.e. either together or separately, or applying compounds I and II sequentially, uses the individual compounds alone. It has been found to provide better control of harmful bacteria than is possible.

  Usually a mixture of compound I and one phenyl hydrazide II is used. However, in some cases, mixtures of compounds I and II with further fungicides may also be advantageous.

  Particularly preferred is compound Ia.

  Due to their basic nature, compounds Ia and Ib can form salts or adducts with inorganic or organic acids, or with metal ions.

  Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid, carbonic acid and nitric acid.

  Suitable organic acids are, for example, formic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkyl Sulfonic acids (sulfonic acids having a linear or branched alkyl group having 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic groups having one or two sulfo groups such as phenyl and Naphthyl), alkylphosphonic acids (phosphonic acids having a linear or branched alkyl group with 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (fragrances having one or two phosphonic acid groups) Group, such as phenyl and naphthyl), an alkyl or aryl group may be further substituted, Example, if p- toluenesulfonic acid, salicylic, p- aminosalicylic acid, 2-phenoxybenzoic acid, it is possible to have a 2-acetoxybenzoic acid or the like.

  Suitable metal ions are in particular group 2 element ions, in particular calcium and magnesium ions, group 3 and group 4 ions, in particular aluminum, tin and lead ions, and group 1 to 8 transition group ions. In particular ions such as chromium, manganese, iron, cobalt, nickel, copper and zinc. Particularly preferred is a metal ion of a transition group element in the fourth period. The metal can be present in various valences that can be expected.

  When preparing the mixture, it is preferred to use purified active compounds I and II, together with further active compounds or pesticide or growth-regulating activity against harmful fungi or other pests such as insects, scabies or nematodes The compound or fertilizer can be mixed when needed.

  Mixtures of compounds I and II or simultaneous or separate use of compounds I and II have significant effects on a wide range of phytopathogenic fungi, especially those from the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes types.

  They are used to control a large number of fungi in various crop plants such as cotton, vegetable species (eg cucumbers, beans and cucumbers), coffee, fruit species, soybeans, vines, ornamental plants, and various seeds. Of particular importance.

  They include the following plant pathogens: Erysiphe cichoracearum and Sphaerotheca fuliginea in the Cucurbitaceae, Podosphaera leucotricha in apples, Uncinula necator in vines, Venturia inaequalis (scab) in apples, Septoria nodorum in wheat, strawberries, vegetables, ornamental plants and grapes Botrytis cinerea in gray trees, Cercospora arachidicola in tuberous plants, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora species in cucurbits and hops, Plasmopara viticola in vines, Alternaria species in vegetables and fruits, and Fusarium and Verticillium It is particularly suitable for controlling species.

  Compounds I and II can be applied simultaneously, i.e. either together or separately, or can be applied sequentially, in the case of separate applications, the order generally results in inhibition. There is no effect.

  Compounds I and II are usually applied in a weight ratio of 100: 1 to 1:10, preferably 10: 1 to 1: 1, especially 5: 1 to 1: 1.

  Correspondingly, the application rate of compound I is usually 5 to 2,000 g / ha, preferably 10 to 1,000 g / ha, in particular 50 to 750 g / ha.

  Depending on the nature of the desired effect, the application rate of the mixtures according to the invention is 5 to 500 g / ha, preferably 50 to 500 g / ha, in particular 50 to 200 g / ha, for compound II.

  For seed treatment, the application rate of the mixture is generally from 0.001 to 1 g / kg of seed, preferably from 0.01 to 0.5 g / kg of seed, in particular from 0.01 to 0.1 g / kg of seed.

  If phytopathogenic harmful fungi are to be controlled, the application of compounds I and II separately or together or the mixture of compounds I and II can be applied before or after sowing or before or after plant emergence. By spraying or sprinkling seeds, plants or soil.

  The bactericidal synergistic mixture or compounds I and II according to the invention are for example in the form of ready-to-spray solutions, powders and suspensions or highly concentrated aqueous, oily or other suspensions, dispersions, emulsions Can be formulated in the form of oil dispersions, pastes, dusts, spraying materials or granules, and can be applied by spraying, atomizing, sprinkling, spraying or sprinkling. The use form depends on the intended purpose and in each case it should be ensured that the mixture according to the invention can be distributed as finely and homogeneously as possible.

  The formulations are produced in a manner known per se, for example by adding solvents and / or carriers. It is customary to mix inert additives such as emulsifiers or dispersants with the formulation.

  Suitable surfactants include aromatic sulfonic acids such as ligno-, phenol-, naphthalene-, and dibutylnaphthalene sulfonic acids and fatty acids, alkyl- and alkylaryl sulfonate esters, alkyl, lauryl ether and aliphatic alcohol sulfate esters. , Alkali metal salts, alkaline earth metal salts and ammonium salts, and sulfated hexa-, hepta- and octadecanol salts or salts of aliphatic alcohol glycol ethers, sulfonated naphthalene and derivatives thereof Condensates with formaldehyde, naphthalene condensates, or condensates of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octyl phenyl ether, ethoxylated isooctyl-, octyl-, or nonylphenol, alkyl Phenyl polyglycol ether or tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, aliphatic alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol poly Glycol ether acetate, sorbitol ester, lignosulfite waste liquor or methylcellulose.

  Powders, materials for dusting and dusts can be produced by mixing Compound I and II or a mixture of Compound I and II with a solid support or by grinding together.

  Granules (eg coated granules, soaked granules or homogeneous granules) are usually produced by binding the active compound (s) to a solid carrier.

  Fillers or solid carriers, for example, mineral soils such as silica gel, silicic acid, silicates, talc, kaolin, limestone, lime, chalk, balls, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground Synthetic materials and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and products of plant origin such as cereal flour, bark flour, wood flour and nutshell flour, cellulose powder or other solid carriers.

  The formulation generally comprises from 0.1 to 95%, preferably from 0.5 to 90% by weight of one of compounds I and II or a mixture of compounds I and II. The active compound is used in a purity of 90-100%, preferably 95-100% (according to NMR or HPLC spectrum).

  Compounds I and II, mixtures or corresponding preparations can be used to kill bacteria, plants, seeds, soils, areas, materials or spaces to be kept free of bacteria, in a mixture effective for sterilization or for separate application. In some cases it is applied by treatment with compounds I and II. Application can be carried out before or after infection by harmful bacteria.

Examples of such preparations containing the active compound are:
I. A solution of 90 parts by weight of active compound and 10 parts by weight of N-methylpyrrolidone; this solution is suitable for use in the form of microdrops;
II. 20 parts by weight of active compound, 80 parts by weight of oxylene, 10 parts by weight of adduct of 8-10 moles of ethylene oxide and 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of dodecylbenzenesulfonic acid A calcium salt, 5 parts by weight of an adduct mixture of 40 moles of ethylene oxide and 1 mole of castor oil; a dispersion is obtained by finely distributing the solution in water;
III. An aqueous dispersion of 20 parts by weight of active compound, 40 parts by weight cyclohexanone, 30 parts by weight isobutanol, 20 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil;
IV. 20 parts by weight of active compound, 25 parts by weight cyclohexanol, 65 parts by weight mineral oil fraction boiling point 210-280 ° C and 10 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil Dispersion;
V. Hammer of 80 parts by weight of active compound, 3 parts by weight of diisobutylnaphthalene-1-sulfonic acid sodium salt, 10 parts by weight of sodium salt of lignosulfonic acid from sulfite waste liquor and 7 parts by weight of finely divided silica gel A milled mixture; by finely distributing the mixture in water, a spray mixture is obtained;
VI. A complete mixture of 3 parts by weight of active compound and 97 parts by weight of finely divided kaolin; this dust contains 3% by weight of active compound;
VII. 30 parts by weight of active compound, 92 parts by weight finely divided silica gel and 8 parts by weight of a complete mixture of paraffin oil sprayed on the surface of this silica gel; this formulation gives good stickiness to the active compound ;
VIII. 40 parts by weight of active compound, 10 parts by weight of sodium salt of phenolsulfonic acid / urea / formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of a stable aqueous dispersion; this dispersion is further diluted Can be;
IX. 20 parts by weight of active compound, 2 parts by weight calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight aliphatic alcohol polyglycol ether, 20 parts by weight sodium salt of phenolsulfonic acid / urea / formaldehyde condensate and 88 A stable oily dispersion of parts by weight of paraffinic mineral oil.

The bactericidal activity of the compounds and mixtures can be demonstrated by the following experiments:
The active compounds were prepared separately or together as a stock solution containing 0.25% by weight of active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol ™ EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and the mixture was diluted with water to the desired concentration.

Example of use: An aqueous suspension with the concentration of the active compounds described below on the leaves of a potted grape of the persistent cultivar "Muller-Thurgau" against grape downy mildew (peronospora) caused by Plasmopara viticola The liquid was sprayed until the droplets dropped. Plants were placed in a greenhouse for 3 days after the spray coating had dried to allow assessment of the persistence of the material. Only then was the leaves inoculated with an aqueous zoospore suspension of Plasmopara viticola. The grapes were then first kept in a steam saturated room at 24 ° C. for 48 hours and then kept in a greenhouse at 20-30 ° C. for 5 days. After this, the plants were placed again in a humid room for 16 hours to promote sporulation. Next, the degree of occurrence of infection on the lower surface of the leaf was measured visually.

  For evaluation, the percentage value of the infected leaf area measured visually was converted to efficacy, expressed as% of the untreated control.

Efficacy ( E ) is the following Abbot formula:
E = (1-α / β) ・ 100
Where α corresponds to fungal infection of treated plants in% and β corresponds to fungal infection of untreated plants in%.

  A potency of 0 means that the level of infection of the treated plant corresponds to the level of infection of the untreated plant; a potency of 100 means that the treated plant was not infected.

The expected potency of the active compound mixture is the formula of Colby (RS Colby, Weeds 15 , 20-22 (1967)):
E = x + y-x · y / 100
Where E is the expected potency as a percentage of the untreated control when a mixture of active compounds A and B is used at concentrations a and b, and x is when active compound A is used at concentration a. The expected potency in% of the untreated control and y is the expected potency in% of the untreated control when active compound B is used at concentration b)
And compared with the observed potency.

  The test results show that for all mixing ratios, the observed potency is higher than expected using the Colby equation.

Claims (8)

A) Phenylhydrazide I selected from compounds Ia and Ib:

When,
B) Formula II:

And a sterilizing mixture comprising a synergistically effective amount of the compound. Fungicidal mixture according to claim 1 comprising a compound I a as claimed in claim 1 as a phenyl hydrazide I.   The sterilizing mixture according to claim 1 or 2, wherein the weight ratio of Compound I to Compound II is 10: 1 to 1: 100.   A bactericidal composition comprising a solid or liquid carrier and the mixture according to claim 1.   A method for controlling harmful fungi, wherein the harmful fungus, its habitat, or a plant, seed, soil, region, material or space to be kept free of the fungus is represented by formula I according to claim 1. And treating with a compound of formula II and a compound of formula II.   Treating a plant, seed, soil, region, material or space to be kept in a harmful fungus, its habitat or in its absence, with 5 to 2000 g / ha of compound II according to claim 1 The method of claim 5.   A plant, seed, soil, region, material or space to be kept in a harmful fungus, its habitat or in its absence, is treated with at least one compound I according to claim 1 of 5 to 500 g / ha. 6. The method of claim 5, comprising:   Use of a compound of formula I and II according to claim 1 for the preparation of a mixture according to claim 1.